CN109920992A - A method of preparing lithium ion battery selenium carbon composite anode material - Google Patents
A method of preparing lithium ion battery selenium carbon composite anode material Download PDFInfo
- Publication number
- CN109920992A CN109920992A CN201910182405.4A CN201910182405A CN109920992A CN 109920992 A CN109920992 A CN 109920992A CN 201910182405 A CN201910182405 A CN 201910182405A CN 109920992 A CN109920992 A CN 109920992A
- Authority
- CN
- China
- Prior art keywords
- carbon composite
- selenium
- lithium ion
- anode material
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of methods for preparing lithium ion battery selenium carbon composite anode material, belong to the technical field of secondary cell in electrochemistry.Heretofore described selenium carbon composite is then prepared through high-temperature heat treatment and step chemical etching reaction using metal organic framework compound as presoma;Selenium carbon composite electrode prepared by the top-down nano-fabrication concept that the present invention uses makes the load site of selenium with very high selectivity and loading content is higher than conventional method, preparation method is simple and effective, prepared selenium carbon composite electrode material shows excellent storage lithium performance, still keeps the high lithium storage content for arriving 280mAh/g after 300 circulations under the current density of 1000mA/g.
Description
Technical field
The invention belongs to the secondary cell fields of electrochemistry, and in particular to a kind of selenium carbon that can be used for lithium ion cell positive
Combination electrode material and preparation method thereof.
Technical background
Lithium ion battery (LIBs) has many advantages, such as that energy density is high, has extended cycle life, operating temperature range is wide, extensive
Applied in all kinds of portable electronic devices.However, with the development of science and technology and social progress, demand of the people to the energy
Increasingly increase, traditional LIBs has been unable to satisfy the actual demand of people.It develops with higher capacity density, longer using the longevity
Life, the novel battery system of more low price have become an important development field.It is close with the Li-S energy content of battery that S does anode
Degree is approximately 2 ~ 5 times of traditional LIBs, and the volume energy density (3467 Wh/L) with superelevation, is the electricity of current great prospect
One of pond body system.But positive electrode S used in Li-S battery system is easily reacted with lithium, forms more sulfur molecules and the more sulphur of lithium
Compound, and lithium polysulfide is soluble in electrolyte, leads to the rapid decaying of battery capacity.In addition, the electric conductivity of sulphur is non-
It is often poor, limit the high rate performance of battery system.Problem above significantly limits the development of Li-S battery.And it is in same with S
The Se of one main group (VI A) constructs novel high-energy battery system for us and provides new thinking.Li-Se battery has high
Theoretical energy density (1155 Wh/kg or 3254 Wh/L), using Se as positive electrode, the volume of resulting Li-Se battery is held
Amount can match in excellence or beauty with Li-S system, furthermore the electric conductivity (1 × 10 of Se-3S/cm) it is much higher than the electric conductivity (5 × 10 of S-30 S/
Cm), to show better electrochemical reaction activity, electrode material utilization and high rate performance, and polysulfide is readily soluble
Similar problems of dissolution can also be improved in Li-Se battery in electrolyte.
There is also problems by Se as other electrode materials, are mainly shown as: there are biggish volumes by Se in circulation
Variation, causes the easy dusting of electrode material, falls off;More selenides intermediates are easily removed from anode in charge and discharge, cause capacity not
Reversible decaying;Ion/electron-transporting of blocky Se is poor, influences the practical efficiency of electrode.Problem above directly limits
The cyclical stability and high rate performance of Li-Se battery.Further increase the cyclical stability and high rate performance of Se electrode
It is the key that promote Li-Se battery applications.Studies have shown that by Se and carbon carry out it is compound prepare nanoscale selenium carbon composite,
The small size advantage of nano material can be effectively played, and volume change of the Se particle in multiple charge and discharge can be limited, also
The electric conductivity that can greatly improve electrode material also plays certain effect to the removing for preventing more selenides.In recent years, domestic
Outer researchers have constructed a large amount of selenium carbon composite to improve the chemical property of Se anode.However, tradition is constructed
The method of selenium carbon composite is generally mentality of designing from bottom to top, i.e., constructs the carbon frame with certain space configuration first
Frame is then melted by heat or the method for high temperature thermal decomposition introduces Se, finally obtains selenium carbon composite.Such is from bottom to top
Preparation method, Se relies primarily on physisorption in the synthesis process and carbon progress is compound, and part Se is inevitably had in product
Assembled in the form of block in the outside of carbon frame, the irreversible decaying easy to fall off to cause capacity in charge and discharge, furthermore according to
The load capacity of selenium is limited (usually less than 60wt%) in the selenium carbon composite prepared by the physisorphtion, it is difficult to give full play to
The material advantage of Se electrode.
Summary of the invention
The present invention in order to realize lithium ion battery at higher current densities capacity retention ratio still with higher and circulation the longevity
Life improves the chemical property of Li-Se battery system, proposes a kind of knot for preparing selenium carbon composite (Se@C) from top to bottom
Structure and preparation method thereof.This method simple possible, is easy to large-scale production at stable structure.
One kind of the invention prepares the specific implementation step of the method for lithium ion battery selenium carbon composite anode material from top to bottom
It is rapid as follows:
(1) it disperses zinc salt, 2-methylimidazole in methanol respectively, zinc solution is while agitating by 2-methylimidazole solution
It is added thereto, stirring or ultrasound are allowed to be uniformly dispersed;Then static ageing for 24 hours, is then centrifuged for separation, drying obtains xeraphium
End;
(2) gained powder in a certain proportion of selenium powder and step (1) is placed in same crucible, Se powder is made to be placed in uptake,
It is heat-treated under conditions of closed by protective gas of inert gas, the heating rate for controlling reaction is 1o/min~10o/ min,
Reaction temperature is 400 ~ 800oC, heat treatment time 2-12h;
(3) the above-mentioned product soaking for preparing is subjected to chemical etching in the solution containing ferric ion, to remove gold therein
Belong to ion, then centrifuge separation, drying obtain dry target product;
Zinc salt described in step (1) is Zn (NO3)2·6H2O、ZnCl2·6H2Or ZnSO O,4·6H2O, and be that analysis is pure;
The molar ratio of 2-methylimidazole described in step (1) and zinc salt is 3:1 ~ 10:1, best proportion 4:1;
Drying steps described in step (1) and step (3) be less than 80 DEG C at a temperature of target product is dry to constant weight;
The mass ratio of added Se powder and step (1) gained powder is 1:1 ~ 5:1 in step (2);
Inert protective gas described in step (2) is argon gas, nitrogen or hydrogen and purity is above 99.9%;
Trivalent iron salt described in step (3) is FeCl3、Fe(NO3)3Or Fe2(SO4)3And purity is that analysis is pure.
The solution concentration of trivalent iron salt described in step (3) is 0.1 ~ 3mol/L, and reaction temperature is room temperature;
The reaction time of chemical etching described in step (3) is 2 ~ 48h;
The present invention is using metal organic framework compound as presoma, using Se powder as selenium source, through Low Temperature Heat Treatment, after chemical etching
To selenium carbon composite, preparation method is simple.Generated in-situ carbonaceous conductive matrix is without additionally introducing in product, carbonaceous conductive matrix
It combines closely with selenium, can guarantee electrode material in multiple charge and discharge process reactivity still with higher and stable structure.
Detailed description of the invention
Fig. 1 is the SEM figure of selenium carbon composite prepared in the embodiment of the present invention 3.
Fig. 2 is is that the Li-Se battery that anode is assembled exists with selenium carbon composite prepared in the embodiment of the present invention 4
Cycle performance figure under 1000mA/g electric current.
Specific embodiment:
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing, but the present invention is not limited to models as described below
It encloses.
Embodiment 1: the method for preparing lithium ion battery selenium carbon composite anode material from top to bottom of the present embodiment is specific
Steps are as follows:
(1) zinc salt chosen is Zn (NO3)2·6H2O, the molar ratio for controlling 2-methylimidazole and zinc salt is 4:1, and stirring is extremely
For 24 hours, product is centrifugated, is dry solution for static hatching after being uniformly dispersed.
(2) gained powder in step (1) and selenium powder are placed in the two sides of same crucible according to the mass ratio of 1:1, and protected
It holds selenium powder and is in tube furnace upwind side, when heat treatment uses argon gas for protective gas, 3oIt heats up under the heating rate of/min
To 550oC simultaneously keeps the temperature 3h, after cooled to room temperature, collects product.
(3) product after above-mentioned heat treatment is impregnated in the liquor ferri trichloridi with 0.5mol/L, is stirred at room temperature, etched
12h.Final product is obtained after product centrifuge separation, forced air drying.
(4) the selenium carbon composite anode material that will be prepared, by Se@C: conductive carbon black: PVDF=80: 10: 10 mass ratio
Example is mixed, and suitable solvent NMP is added, is mixed, is applied on aluminium foil, is subsequently transferred to 100 in vacuum ovenoC
Lower vacuum drying 8h, is made anode;Use metal lithium sheet for cathode;The LiPF6 that electrolyte is 1mol/L dissolves EC:DEC:
The in the mixed solvent (volume ratio 1: 1: 1) of DMC is assembled into 2032 button cells in the glove box full of argon gas.To preparation
Good button cell carries out charge-discharge test.Test result confirm the selenium carbon composite anode material for preparing under this condition show compared with
High charge/discharge capacity, first all charge/discharge capacities are respectively 450mAh/g and 480mAh/g under the current density of 100mA/g.
Embodiment 2: the method for preparing lithium ion battery selenium carbon composite anode material from top to bottom of the present embodiment is specific
Steps are as follows:
(1) zinc salt chosen is ZnSO4·6H2O, the molar ratio for controlling 2-methylimidazole and zinc salt is 6:1, stirring to solution
24 h of static hatching after being uniformly dispersed, product centrifuge separation, drying.
(2) gained powder in step (1) and selenium powder are placed in the two sides of same crucible according to the mass ratio of 1:4, and protected
It holds selenium powder and is in tube furnace upwind side, when heat treatment uses nitrogen for protective gas, 5oIt heats up under the heating rate of C/min
To 600oC simultaneously keeps the temperature 2h, after cooled to room temperature, collects product.
(3) product after above-mentioned heat treatment is impregnated to the Fe (NO with 1.0mol/L3)3It in solution, stirs at room temperature, etches 7h.
Final product is obtained after product centrifuge separation, forced air drying.
(4) the selenium carbon composite anode material that will be prepared, by Se@C: conductive carbon black: PVDF=80: 10: 10 quality
Ratio is mixed, and suitable solvent NMP is added, is mixed, is applied on aluminium foil, is subsequently transferred in vacuum oven
100oIt is dried in vacuo 8h under C, anode is made;Use metal lithium sheet for cathode;The LiPF6 that electrolyte is 1mol/L dissolves EC:
The in the mixed solvent (volume ratio 1: 1: 1) of DEC:DMC is assembled into 2032 button cells in the glove box full of argon gas.It is right
The button cell prepared carries out charge-discharge test.
Embodiment 3: the method for preparing lithium ion battery selenium carbon composite anode material from top to bottom of the present embodiment is specific
Steps are as follows:
(1) zinc salt chosen is ZnCl2·6H2O, the molar ratio for controlling 2-methylimidazole and zinc salt is 3.75:1, and stirring is extremely
Solution 24 h of static hatching after being uniformly dispersed, product centrifuge separation, drying.
(2) gained powder in step (1) and selenium powder are placed in the two sides of same crucible according to the mass ratio of 1:2, and protected
It holds selenium powder and is in tube furnace upwind side, when heat treatment uses nitrogen for protective gas, 3oIt heats up under the heating rate of/min
To 500oC simultaneously keeps the temperature 4h, after cooled to room temperature, collects product.
(3) product after above-mentioned heat treatment is impregnated in the liquor ferri trichloridi with 2.0mol/L, is stirred at room temperature, etched
5h.Final product is obtained after product centrifuge separation, forced air drying.
(4) image is carried out to the selenium carbon composite synthesized under this method and morphology analysis, resulting SEM is as shown in Figure 1.
Product prepared by this method is the polyhedral structure that size is about 500nm and outside is uniformly enclosed with carbon-coating, outside polyhedron
Portion there are no the presence of absorption granules of selenium, it was demonstrated that selenium can be uniformly wrapped in carbon-coating by the top-to-bottom method products therefrom
Portion, XRD analysis confirms the product under the embodiment there is only the diffraction maximums of selenium and carbon exist without other image, further after analysis
The content for confirming selenium in products therefrom under this method is 66wt%.
(5) the selenium carbon composite anode material that will be prepared, by Se@C: conductive carbon black: PVDF=80: 10: 10 quality
Ratio is mixed, and suitable solvent NMP is added, is mixed, is applied on aluminium foil, is subsequently transferred in vacuum oven
100oIt is dried in vacuo 8h under C, anode is made;Use metal lithium sheet for cathode;The LiPF6 that electrolyte is 1mol/L dissolves EC:
The in the mixed solvent (volume ratio 1: 1: 1) of DEC:DMC is assembled into 2032 button cells in the glove box full of argon gas.It is right
The button cell prepared carries out charge-discharge test.Test result shows that selenium carbon composite prepared by the embodiment is shown
Excellent high rate performance still maintains the capacity of 200mAh/g under the current density of 3000mA/g.
Embodiment 4: the method for preparing lithium ion battery selenium carbon composite anode material from top to bottom of the present embodiment is specific
Steps are as follows:
(1) zinc salt chosen is ZnNO3·6H2O, the molar ratio for controlling 2-methylimidazole and zinc salt is 5:1, stirring to solution
24 h of static hatching after being uniformly dispersed, product centrifuge separation, drying.
(2) gained powder in step (1) and selenium powder are placed in the two sides of same crucible according to the mass ratio of 1:2, and protected
It holds selenium powder and is in tube furnace upwind side, when heat treatment uses argon gas for protective gas, 2oIt heats up under the heating rate of/min
To 500oC simultaneously keeps the temperature 3h, after cooled to room temperature, collects product.
(3) product after above-mentioned heat treatment is impregnated in the liquor ferri trichloridi with 1.0mol/L, is stirred at room temperature, etched
12h.Final product is obtained after product centrifuge separation, forced air drying.
(4) image and morphology analysis, product prepared by this method are carried out to the selenium carbon composite synthesized under this method
It is similar to embodiment 3 for pattern, but polyhedral space structure keeps more intact, no disrepair phenomenon.XRD analysis confirms should
Also there is only the diffraction maximums of selenium and carbon exists without other image for product under embodiment, further confirms institute under this method after analysis
The content for obtaining selenium in product is up to 67wt%.
(5) the selenium carbon composite anode material that will be prepared, by Se@C: conductive carbon black: PVDF=80: 10: 10 quality
Ratio is mixed, and suitable solvent NMP is added, is mixed, is applied on aluminium foil, is subsequently transferred in vacuum oven
100oIt is dried in vacuo 8h under C, anode is made;Use metal lithium sheet for cathode;The LiPF6 that electrolyte is 1mol/L dissolves EC:
The in the mixed solvent (volume ratio 1: 1: 1) of DEC:DMC is assembled into 2032 button cells in the glove box full of argon gas.It is right
The button cell prepared carries out charge-discharge test.Test result shows that selenium carbon composite prepared by the embodiment is shown
Excellent high rate performance and good cyclical stability still maintain after 300 circle circulations under the current density of 1000mA/g
The capacity of 280mAh/g.
The present invention is a kind of method for preparing selenium carbon composite electrode material from top to bottom, and this method selects first and Se has
Compared with centered on the metal ion of strong affinity (M) and selected metal ion have coordinate force organic molecule be ligand, preparation
Metal organic framework compound presoma at low temperature sends out Se and metal organic framework compound then using Se powder as selenium source
Raw reaction prepares metal selenide cladding carbon structure (MSe C), finally removes metal M using the method for chemical etching, obtains mesh
Target selenium carbon composite (Se@C).The top-down synthetic method can effectively overcome tradition to prepare selenium carbon composite
The presence that block Se is adsorbed in method, ensure that Se there are the selectivity that site has height, and prepare containing for Se in product
It measures higher (> 60wt.%).
The process for only illustrating the principle of the present invention and most preferred embodiment described in description above and case study on implementation, not
It is detached from the case of actual conditions and principle of the present invention, the present invention can also be attempted using other metallic compound frames, these changes
Change and improvement is both fallen within the scope of claimed invention.
Claims (9)
1. a kind of method for preparing lithium ion battery selenium carbon composite anode material, which comprises the following steps:
(1) it disperses zinc salt, 2-methylimidazole in methanol respectively, zinc solution is while agitating by 2-methylimidazole solution
It is added thereto, stirring or ultrasound are allowed to be uniformly dispersed;Subsequent static ageing is then centrifuged for separation, drying obtains dried powder;
(2) gained powder in a certain proportion of selenium powder and step (1) is placed in same crucible, Se powder is made to be placed in uptake,
It is heat-treated under conditions of closed by protective gas of inert gas, the heating rate for controlling reaction is 1o/min ~ 10o/
Min, reaction temperature are 400 ~ 800 oC, heat treatment time 2-12h;
(3) the above-mentioned product soaking for preparing is subjected to chemical etching in the solution containing ferric ion, to remove gold therein
Belong to ion, then centrifuge separation, drying obtain dry target product.
2. a kind of method for preparing lithium ion battery selenium carbon composite anode material according to claim 1, feature exist
In,
The reaction time of chemical etching described in step (3) is 2 ~ 48h.
3. a kind of method for preparing lithium ion battery selenium carbon composite anode material according to claim 1, feature exist
In zinc salt described in step (1) is Zn (NO3)2·6H2O、ZnCl2·6H2Or ZnSO O,4·6H2O, and be that analysis is pure.
4. a kind of method for preparing lithium ion battery selenium carbon composite anode material according to claim 1, feature exist
In the molar ratio of 2-methylimidazole described in step (1) and zinc salt is 3:1 ~ 10:1, best proportion 4:1.
5. a kind of method for preparing lithium ion battery selenium carbon composite anode material according to claim 1, feature exist
In, drying steps described in step (1) and step (3) be less than 80 DEG C at a temperature of target product is dry to constant weight.
6. a kind of method for preparing lithium ion battery selenium carbon composite anode material according to claim 1, feature exist
In the mass ratio of added Se powder and step (1) gained powder is 1:1 ~ 5:1 in step (2).
7. a kind of method for preparing lithium ion battery selenium carbon composite anode material according to claim 1, feature exist
In inert protective gas described in step (2) is argon gas, nitrogen or hydrogen and purity is above 99.9%.
8. a kind of method for preparing lithium ion battery selenium carbon composite anode material according to claim 1, feature exist
In trivalent iron salt described in step (3) is FeCl3、Fe(NO3)3Or Fe2(SO4)3And purity is that analysis is pure.
9. a kind of method for preparing lithium ion battery selenium carbon composite anode material according to claim 1, feature exist
In,
The solution concentration of trivalent iron salt described in step (3) is 0.1 ~ 3mol/L, and reaction temperature is room temperature.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910182405.4A CN109920992A (en) | 2019-03-12 | 2019-03-12 | A method of preparing lithium ion battery selenium carbon composite anode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910182405.4A CN109920992A (en) | 2019-03-12 | 2019-03-12 | A method of preparing lithium ion battery selenium carbon composite anode material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109920992A true CN109920992A (en) | 2019-06-21 |
Family
ID=66964339
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910182405.4A Withdrawn CN109920992A (en) | 2019-03-12 | 2019-03-12 | A method of preparing lithium ion battery selenium carbon composite anode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109920992A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111244445A (en) * | 2020-01-16 | 2020-06-05 | 中南大学 | Lithium-sulfur battery composite positive electrode active material and preparation and application thereof |
CN111463406A (en) * | 2020-04-09 | 2020-07-28 | 江苏师范大学 | Preparation method of cobalt-doped zinc-based metal selenide composite electrode for lithium ion battery |
CN112909259A (en) * | 2021-02-04 | 2021-06-04 | 陕西科技大学 | Method for preparing carbon nanotube material catalytically grown from FeNi alloy by electromagnetic induction heating method |
CN117832501A (en) * | 2024-03-05 | 2024-04-05 | 唐山师范学院 | Porous carbon composite battery electrode material and preparation method thereof |
-
2019
- 2019-03-12 CN CN201910182405.4A patent/CN109920992A/en not_active Withdrawn
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111244445A (en) * | 2020-01-16 | 2020-06-05 | 中南大学 | Lithium-sulfur battery composite positive electrode active material and preparation and application thereof |
CN111244445B (en) * | 2020-01-16 | 2021-04-27 | 中南大学 | Lithium-sulfur battery composite positive electrode active material and preparation and application thereof |
CN111463406A (en) * | 2020-04-09 | 2020-07-28 | 江苏师范大学 | Preparation method of cobalt-doped zinc-based metal selenide composite electrode for lithium ion battery |
CN111463406B (en) * | 2020-04-09 | 2022-03-25 | 江苏师范大学 | Preparation method of cobalt-doped zinc-based metal selenide composite electrode for lithium ion battery |
CN112909259A (en) * | 2021-02-04 | 2021-06-04 | 陕西科技大学 | Method for preparing carbon nanotube material catalytically grown from FeNi alloy by electromagnetic induction heating method |
CN117832501A (en) * | 2024-03-05 | 2024-04-05 | 唐山师范学院 | Porous carbon composite battery electrode material and preparation method thereof |
CN117832501B (en) * | 2024-03-05 | 2024-05-24 | 唐山师范学院 | Porous carbon composite battery electrode material and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107226475B (en) | Potassium ion battery positive electrode material, preparation method thereof and potassium ion battery | |
CN109920992A (en) | A method of preparing lithium ion battery selenium carbon composite anode material | |
CN110474044A (en) | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof | |
CN101719546A (en) | Method for preparing lithium ion battery anode material doped with nanometer oxide | |
CN106340633B (en) | A kind of high performance lithium ion battery composite nano materials and preparation method thereof | |
CN110176601A (en) | Carbon-coated silicon monoxide negative electrode material and preparation method and application thereof | |
CN104037412B (en) | The preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball | |
CN108183213B (en) | Preparation method of ferric oxide/carbon nanotube lithium ion battery cathode material | |
CN106981643B (en) | A kind of method that biogel carbonization prepares the double-deck carbon coating manganous oxide electrode material | |
CN109873134A (en) | Iron-based chalcogenide, electrode material, the sodium-ion battery and preparation method thereof of in-situ carbon encapsulation | |
CN106531986B (en) | A kind of titanium nitride/silicon nitride/carbonitride/graphene composite nano material and preparation method thereof | |
CN107317001A (en) | A kind of artificial gold/N doping carbonization bacteria cellulose lithium ion battery negative material and preparation method thereof | |
CN110504424A (en) | A kind of two iron lithium ion battery negative material of porous spherical phosphatization and preparation method thereof | |
CN106887572A (en) | A kind of antimony carbon composite and its preparation method and application | |
CN109888236B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
CN108110242A (en) | A kind of preparation method of lithium ion battery nickel manganese cobalt composite material | |
CN109279663B (en) | Borate sodium-ion battery negative electrode material and preparation and application thereof | |
CN110459768A (en) | A kind of octahedral structure iron phosphide/carbon composite and the preparation method and application thereof | |
CN101920953B (en) | Preparation method of spherical anode material LiVPO4F | |
CN107959024A (en) | A kind of sodium-ion battery anode sheet Sb2Se3Nanocrystalline preparation method | |
CN107845787B (en) | Pomegranate-shaped Fe3O4Preparation method of @ N-C lithium battery negative electrode material | |
CN113471421B (en) | Preparation method of composite positive electrode material of lithium-sulfur battery | |
CN105206824B (en) | A kind of preparation method of height ratio capacity lithium-rich anode material | |
CN112002893B (en) | Research of taking antimony-based composite metal sulfide as potassium ion battery negative electrode material | |
CN108539146A (en) | A kind of lithium ion battery composite cathode material and the preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190621 |